Laundering compositions containing ortho-phosphoric acid esters



e r 2,758,093 Icg Patented Aug. 7, 1955 LAUNDERING COMPOSITIONS CONTAINING ORTHO-PHOSPHORIC ACID ESTERS Robert Ernst and George D. Loetf, Los Angeles, Calif., assignors to Textilana Corporation, Hawthorne, Calitl, a corporation of California No Drawing. Original application June 22, 1948, Serial No. 34,569, now Patent No. 2,656,372, dated October 20, 1953. Divided and this application August 31, 1953, Serial No. 377,684

12 Claims. (Cl. 252-452) This application is a division of application Serial No. 34,569, filed June 22, 1948, now Patent No. 2,656,372.

This invention relates to surface active compounds having foaming and emulsifying properties, and particularly to the salts of alkyl acid esters of orthophosphoric acid.

We have discovered that certain of the salts of the normal octyl and normal decyl acid esters of orthophosphoric acid having the unique and unexpected properties of being both frothing and emulsifying agents as well as wetting agents. Unlike the salts of the other alkyl acid phosphates, whether they be meta, pyro, or poly phosphates, such as tri poly and tetra poly phosphates, either in the form of mono or dialkyl esters or mixed mono and dialkyl esters, such compounds have both frothing, wetting and emulsifying action. Whereas many of the above salts have good surface activity in reducing surface tension of water and others have good emulsifying properties, none but the above salts of the normal octyl and normal decyl mono and di ortho-phosphoric acid salts have surface activity, emulsifying property, and also frothing property.

It is therefore entirely unexpected to find among the alkyl acid esters of the phosphoric acids that only the ortho-phosphates, and among them only those in which the alkyl substituent is of the normal Ca and C10 alkyl groups derived by esterification with normal primary octyl or normal primary decyl alcohols, have all of these properties in one compound.

The salts which have such high surface activity and good froth forming and emulsifying properties are the water soluble, alkali metal, ammonium, amine or alkanolamine salts of normal alkyl ortho-phosphoric acid containing mixtures of diacid and mono acid esters of such composition as to comply with the formula where R is normal octyl or normal decyl where the ester linkage, i. e., CO linkage, is on the terminal carbon in which m is ideally 1.5 and preferably within the range of about 1.3 to 1.7 for practical utility.

As stated previously, we have found that where we employ a mixture of the primary (mono) and secondary (di) esters of the specified alkyl phosphoric acid we obtain salts of the above nature which have the desirable balanced properties referred to above.

In order to obtain such mixed mono and di esters we have found it desirable to 'esterify P205 using a ratio of P205 to primary normal alkanol ideally of 1 mol of P20 to 3 mols of alkanol. It is also desirable to assure complete conversion of the P205. The solid residue remaining after the reaction is the result of incomplete conversion, and may be by-products in the form of the esters of phosphoric acid, other than ortho, which as is here shown, are inferior for our purpose, and also of unreacted alcohols. The deviation of the normal value from the ideal 1.5 is a measure of this contamination by side reactions. When carried outwith the ideal mol ratio of 3:1,

as specified, and by carrying the reaction to completion, "111 will equal 1.5. However, useful results can be obtained, as indicated above, if the value is within the range of about 1.3 to about 1.7. Within this range the degree of contamination by-products, other than the mono and diortho-phosphoric esters, as specified above, will however, produce commercially useful products, although their frothing and/ or emulsifying properties are inferior to that of the product wherein the m value more closely approximates 1.5. This variation in m value is obtained by varying the mol ratio of the alcohol to P205 and/ or by regulating the degree of reaction. In such cases Where any unreacted P205 is present it may be removed from the ester or the resulting salt by filtration, centrifuging or settling. It is desirable to exclude the formation of pyrophosphoric, polyphosphoric or metaphosphoric acid esters, either completely :or in any material proportion, by controlling the reaction to give m values as indicated above.

To carry out this esterification, we add P205 in small proportions to the required amount of primary normal alkanol in a jacketed container. The reaction is vigorous and exothermic and should be cooled by circulation of cooling fluid. When all of the P205 has been added the mixture may be heated to a temperature preferably below 200 F. for a period of 2 to 4hours until no solids remain. Light colored products are thus produced, whereas superheating above 200 F, and particularly above 220 F., will result in dark and less desirable esters. The process of esterification may be followed by titration of reactants, adjusting and testing continued until the titratable hydrogen gives an in value of about 1.5 or within the ange of 1.3 to 1.7.

The acid hydrogen in this compound is replaceable by any other cation. We have found, however, that the alkali metal, ammonium, and organo amine ions are the most useful for our purposein forming the salts which will have the frothing action as well as the emulsifying and wetting action which is desirable for a good laundering reagent.

Thus, We may form the sodium, potassium, lithium, or ammonium soap of these acid esters. The organo amine salts are formed from organo amines and have substantial water solubility, such as the alkyl amines, heterocyclic amines, alkanol amines, or other organo amines and their substitution produces and the commercially available mixtures of such amines. Thus, we may use the primary amine salts, such as the salts obtained by neutralization with the primary, secondary, and tertiary alkyl amines, such as methylamine, dimethylamine, ethylamine, trimethylamine, diethylamine, 'triethylamine, monobutylamine, isobutylarnine, secbutylamine, 1,3-diaminobutane, namylamine, sec-amylamine, diethylamine, propylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine (1,2-diaminopropane), l,3-dis-ethylamino butane; alkanolamines such as mono ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, dimethylethanolamine, monoisopropanolamine, di-isopropanolamine, tri-isopropanolamine, butylethanolamine, butyldiethanolamine, N-acetyl ethanolamine, ethylethanolamine, ethyldiethanolamine, 4- arnino-2-butanol, 2-amino-1-butanol, 2-amino-2-methyl-1- propanol, 2-a1nino-2-methyl-l, 3-propanediol, Z-amino-Z- ethyl-l, 3-propanediol, ,tris (hydroxy-methyl) aminomethane, and the heterocyclic amines such as morpholine.

The unique properties of these compounds are of par:

3 wet the soil and the soiled material being laundered; they should have a good frothing action not only in amount but in foam stability; they should have a good detergency, that is, they should emu'lsify the dirt and the grease which is bound'with'the dirt, and. have the property of keeping the dispersion (i. e., the soil) in stable suspension.

The foam and the emulsion stability should be suc'h'that even'when thewater is quiescent, the emulsified soil and the frothed-out soil will be removed by flotation or as an emulsion during draining of the water and not be re-depositedon the material being laundered. The material must have these properties in a highly efficient manner in reagent concentrations as low as to 0.1% by weight of the water.

' The importance of these properties will be clear when i laundering tub without redepositing on'tlie material being washed.

- The test is performed in the following manner: .05 gram of the compound to be tested is dispersed in- 100 cc. distilled water at a temperatureof about 75 F.; 20 cc. of this dispersion (which should be clear and free of precipitates as above described) are placed in a 100-cc.

- cylindrical graduate having an inner diameter of 2.6 cm. and stoppered- The distance between the bottom of the stopper and the bottom of the graduate is. '25 cm. .It is placed upon an eccentric shakerdesigned and oper ated-ata speed to give an agitation which simulates the attention is paid to the characteristics of the laundering operation. The laundering tub or wash reel is rotated in action of the water in a laundering-wheeL. I

The agitating device is a shaker bar, one end of which carries a bearing in which an eccentric pin is journalled.

The eccentric pin is mounted on an eccentric which is rotated'by a shaft whose axis is 2.5 cm. fromthe axis one direction and then is reversed, i. e., it oscillates around its axis of rotation. .This agitates the water and permits the water'to wash over all portions of the cloth; During this period the water must remove the soil. To do this, washing agents must aidthe Water to penetrate into the interstices of the cloth and to emulsify the dirt. These cloth, and specking of the cloth occurs. The emulsion of the hydrophobic material must also be sufiiciently stable I so that the emulsion does not break during-the draining period to deposit the emulsified material on the washed cloth.

It is for this purpose that it is desired to have a washing agent which is a good wetting agent, a good emulsifier, and a good frothing agent. It is, of coursawell recognized that all good wetting agents; i: -e.,. good'surface tension reducers, are not I good frothing agents and good emulsifiers.

We have found by practical and laboratory tests that in order to obtain those salts of the above acid, i. e., to obtain the mono and diorthophosphate esters having the desirable frothing, wetting and emulsifying action which makes them useful as frothing, emulsifying, and wetting agents in laundering operations, we should choose those compounds which are dispersible in an amount of .05% by weight or more in distilled water at room temperature; that is, when .05 grams are placed in 100 cc. distilled water and vigorously shaken, the liquid fraction should be clear and have substantially no visible precipitate. We have found that those phosphate ester salts which have this dispersibility are also dispersible in much greater amounts of say 5% by weight and even are miscible in all proportions, while those which are not so dispersible to the degree of .05% are substantially not dispersible at all.

We have found that the ester salts which have the desirable properties herein described are the salts whose dispersibility in 100 cc. of distilled water at ordinary temperature (75 F.) is of about .05 gram dry solids in such 100 cc. We term such a salt a water dispersible salt.

We also have found by practical and laboratory tests and observations that those salts which have the desirable frothing action which makes them superior laundering agents in home and commercial laundering establishments are those which, when tested by the following test, show at least 5% of the liquid phase foamed out after minutes of quiescence. When such a material is employed in laundering operations, and the laundry wheel has finished its agitation and has been stopped to drain the dirty water, the foam will be sufiiciently stable to keep the dirt in suspension to be withdrawn from the of the eccentric pin. The throw of the eccentric is thus 2.5 cm. The other end of the :bar carries a shaft which is slidably mounted in a hearing. The bearing is mounted on an arm which is pivoted at one end. The distance between the pivot axis and theaxis of .the slidably mounted shaft is 9 cm. The lengthof the line connecting the axis of. the eccentric pin at top dead-center position with a vertical passing through theupivot, 48.2 cm,; that is,

when the pin .is at top deadcenter and the'pivoted arm on .which the bar is mounted is vertical, the top surface of the shaker bar is at an angle of 850 from the horizontal.

. An'upstanding rod is mounted perpendicularly to the top bar.

surface of the shaker bar 21.3 cm... from the axis of the eccentric pin measured along'the bar. A clamp mounted on the rodclamps the vessel to be shaken to the shaker It will be seen that on each rotation of the eccentric pin the rod and the, vessel will traverse an egg-shaped or ovoid path; that is, a path of a distorted ellipse. The graduate is mounted on the shaker bar with its axis 21.3 cm. from the eccentric pin (at top dead-center) and the eccentric rotated at 120 R. P. M..for one minute and then stopped. I

After agitation for the prescribed period, the graduate is allowed to rest for a period after discontinuance of agitation, and the liquid volume (the unfrothed volume) is read after 1 minute, after 5 minutes, and. after 10 minutes next after the discontinuance of agitation.

Practical experience and laboratory tests have shown that those salts which, after 10 minutes standing as above, show at least 2% and preferably 5% liquid phase frothed out, i. e., not more than 19.6 cc. and preferably 19 or less of liquid remaining, will have the desirable frothing action. We term these compounds which pass this test a foaming or stable foam-forming compound, and if they do not pass this test we call them a non-foaming or unstable foam-forming compound.

In addition we have found that while many reagents will disperse grease, oil, or fatty particles and other hydrophobic particles in water which is agitated, the dispersions are unstable and the dispersed particles settle out on the clothes being cleaned when agitation is stopped. We have found by practical and laboratory tests that those salts of the acid esters of the phosphoric acids which in the following tests for dispersions are stable for 1 hour will when used in home and commercial laundering machines keep the dispersed matcrial emulsified and dispersed in the water during that period after the stoppage of the laundering and during the drain period.

The test is performed in the following manner: disperse 5 grams of solid salt in cc. of distilled water in a 500 cc. Erlenmeyer flask and add 45 grams of U. S. P. light mineral oil dyed to a deep shade of red with an oil soluble dye. The stoppered flask is set on the above shaker, shaken for 60 seconds at R. P. M. After agitation is stopped the dispersion is examined visually in a good light. A well dispersed oil will show no distinguishable droplets of oil. Any drops due to its color and the difference in the index of refraction between the oil, and waterare easilydistinguished even if minute.

If no drops are distinguishable; the dispersion is complete. The flask is allowedftd rest for 1 hour. Inorder for-the salt to have adequate emulsifying properties, it should show a complete dispersion. No droplets are to be distinguishable after resting for 20' minutes and preferably 30 minutes.

It has been found that if it is so stable for 30 minutes, it is a stable emulsion and will remain stable for 1 hour or more, and'if so stable it is termed a stable emulsion and the compound is suitable for our purpose.

We term those compounds which do not give such stable dispersions non-emulsifying or unstable emulsionforming compounds, and those which do' givesuch stable emulsion emulsifying or stable emulsion-forming compounds.

We have also found that the salts which have the above desirable frothing and emulsifying action will also, when dispersed in distilled water, have a surface tension of 40 dynes/cm. or less and preferably less than 35 dynes/cm. and are then good surface tension depressants, i. e., good wetting agents. The surface tension tests are made by dispersing .1 gram of the salt in 100 cc. distilled water. If the material does not completely disperse, the clear liquid is removed and tested on a de Nouy Tensiometer.

In practical laundering operations, no one reagent in the prior art has the balanced properties. for good wetting, foam stability, emulsifying stability and detergency action required for practical operation. It has always been necessary to compound enough of such agents to get a balanced formulation. It is therefore a matter of considerable surprise and entirely unexpected to find them all in certain salts of certain alkyl acid esters and thatv such compounds have in balance the requisite frothing, emulsifying and wetting action.

In the following tables are given the characteristics of,

a number of these salts which we have found effective when tested according to the above procedures. For comparison we also tabulate similar salts of other phosphoric acid esters.

TABLE I Salt J.Diethanolamine salt of mono and di n-propyl ortho-phosphoric acid; pale amber liquid; .05 gram dispersible in 100 cc. water.

Salt 2.2-amino-2-methyl-1-propanol salt of mono and di n-propyl ortho-phosphoric acid; clearx stiff paste; .05 gram dispersible in 100 cc. water.

Salt 3.Amm0nia salt of mono and di n-butyl orthophosphoric acid; light amber paste; .05 gram dispersible in 100 cc. water.

Salt 4.Diethanolamine salt of mono and di n-butyl ortho-phosphoric acid; clear viscous liquid; .05 gramdispersible in 100 cc. water.

Salt 5.Ethylene diamine salt of mono and di n-butyl ortho-phosphoric acid; ivory paste; .05 gram dispersible in 100 cc. water.

Salt 6.-2-amino-2-methyl-l-propanol salt of mono and di n-hexyl ortho-phosphoric acid; .05 gram dispersible in 100 cc. water.

Salt 7 .-Sodium salt of mono and di cyclohexyl orthophosphoric acid; white waxy solid; .05 gram dispersible in 100 cc. water.

Salt 8.2 -amino-2-methyl-l-propanol salt of mono and di cyclohexyl ortho-phosphoric acid; white waxy solid; .05- gram dispersible in 100 cc. water.

Salt 9.fiSodium salt of di isoamyl pyrophosphoric acid; .05 gram dispersible in 100 cc. water.

Salt 10.2-amino 2 methyl 1'- propanol salt of di isoamyl pyro-phosphoric acid; amber paste; .05 gram dispersible in 100 cc. water.

Salt 11.Sodium salt of di n-octyl pyrophosphoric acid; clear paste; .05 gram dispersible in 100 cc. water.-

Salt 12.2-amino-2-methyl--1-propanol salt of di noctyl pyrophosphoric acid; ivory paste; .05 gram dispersible in 100. cc. water. I

Salt 13.S odium salt of penta n-octyl-tripolyphosphoric acid; .05 gram dispersible in cc. water.

Salt J4.2-amino2-methyl- I-propanol salt of penta noctyl tripolyphosphoric acid; ivory paste; .05 gram dispersible in 100 cc. water.

Salt 15.Sodium salt of mono and di n-octyl orthophosphoric acid; white stiff paste; .05 gram dispersible in 100 cc. water.

Salt 16.Potassium salt of mono and di no-octyl' orthophosphoric acid; pale ivory paste; .05 gram dispersible in 100 cc. water.

Salt 17.-Ammonium salt of mono and di n-octyl orthophosphoric acid; white waxy paste, semi-solid; .05 gram dispersible in 100 cc. water.

Salt 18.Diethylamine salt of mono and di n-octyl ortho-phosphoric acid; white paste; .05 gram dispersible in 100 cc. water.

Salt 19.-Isopropylamine salt of mono and di n-octyl orthophosphoric acid; white paste; .05 gram dispersible in 100 cc. water.

Salt 20.-n-octylamine salt of mono and di n-octyl orthophosphoric acid; white paste; .05 gram not dispersible in 100 cc. water.

Salt 21.2-amino-2-methyl-1-propanol salt of mono and di n-octyl orthophosphoric acid; white soft waxy solid; .05 gram dispersible in 100 cc. water.

Salt 22.Diethanolamine salt of mono and di n-octyl orthophosphoric acid; clear viscous liquid; .05 gram dispersible in 100 cc. water.

Salt 23.Di and tri propanolamine salt of mono and di n-octyl orthophosphoric acid; clear amber viscous liquid; .05 gram dispersible in 100 cc. water.

Salt 24.-Morpholine (tetrahydro-l, 4-oxazine)' salt of mono and di n-octyl orthophosphoric acid; clear balsamic paste; .05 gram dispersible in 100 cc. water.

Salt 25.Sodium salt of mono and di n-decyl orthophosphoric acid; white waxy solid; .05 gram dispersible in 100 cc. water.

Salt 26.Potassium salt of'mono and di n-decyl orthophosphoric acid; white waxy solid; .05 gram dispersible in 100 cc. water.

Salt 27.Ammonium salt of mono and di n-decyl orthophosphoric acid; white waxy solid; .05 gram dispersible in 100 cc. water.

Salt 28.-Butylamine salt of mono and di n-decyl orthophosphoric acid; white paste; .05 gram dispersible in 100 cc. water.

Salt 29.,Diethanolamine salt of mono and di n-decyl orthophosphoric acid; ivory paste; .05 gram dispersible in 100 cc. water.

Salt 30.-Ammonium salt of mono and ,di n-tetradecyl orthophosphoric acid; white waxy solid; .05 gram dispersible in 100 cc. water.

Salt 31.-Sodium salt of mono and di n-tetradecyl orthophosphoric acid; white Waxy solid; .05 gram dispersible in 100 cc. water.

Salt 32.Potassiurn salt of mono and di n-tetradecyl orthophosphoric acid; white waxy solid; .05 gram dispersible in 100 cc. water.

Salt 33.Diethanolamine salt of mono and di n-tetradecyl orthophosphoric acid; light amber, stiff paste; .05 gram dispersible in 100 cc. water.

Salt 34.Sodium salt of mono and di n-lauryl orthophosphoric acid; ivory waxy solids; .05 grams dispersible in 100 cc. water.

Salt 35'.'Potassium salt of mono and di lauryl orthophosphoric acid; white waxy solids; .05 gram dispersible in 100 cc. water.

Salt 36.-Ammonium salt of mono and di lauryl orthophosphoric acid; ivory waxy solids; .05 gram dispersible in 100 cc. water.

Salt '37.Monoethylamine salt of mono and di lauryl orthophosphoric acid; ivory waxy solids; .05 gram dispersible in 100 cc. water.

Salt 38.+2-amino'-2-methyl-l-propanol salt of mono and di lauryl orthophosphoric acid; tan stiif paste; .05 gram dispersible in 100 cc. water.

Salt 39.Sodium salt of mono and di cetyl orthophosphoric acid; white waxy solids; .05 gram dispersible in 100 cc. water.

Salt 40.-Potassium salt of mono and di cetyl orthophosphoric acid; tan waxy solids; .05 gram dispersiblc in 100 cc. water.

Salt 41.-Ammonium salt of mono and di cetyl orthophosphoric acid; tan waxy solids (soft); .05 gram dispcrsible in 100 cc. water.

Salt 42.-Diethanolamine salt of mono and di cetyl orthophosphoric acid; tan paste; .05 gram dispersible in 100 cc. water.

Table l-A Surface Foaming after- M incl-Al Salt No. tension, oil e1nu1- dyJcm. sification 1H Percent Percent Percent 64. 34 None None None Fails. 68. 40 None None None Do. 56. 30 None None None Do. 59. 60 None None None Do. 57. 50 None None None Do. None None None Do. 49. 90 3% 2 None Do. 49. 84 2% None None Do. 48. 50 2% None None Do. 44. 36 2% None None Do. 38. 2 None None D0. 33. 27 1% 1% None Do. 30. 80 2 None None Do. 32. 03 6% 5 None Do. 34. 33 None None None Do. 34. 45 5 2% 2 Passes 27. 40 50 10 5 730. 33. 20 8% 6% Do. 32.80 33% 11% 8% Do. 52. 1% 1 None Fails. 27. 23 55 10 5 Passes 32. 30 27 7 5 Do. 37. 00 22% 9. 5 7. 5 Do. 33. 23% 7. 5 6% Do. 28. 5 None None None Falls. 27. 36 30 9 5 z Passes 33. 23 22. 5 7 5 D0. 29. 93 7. 5 5 5 D0. 30. 70 4O 12% 6 D0. 45. 96 None None None Fails. 60. 77 None None None Do. 55. 46 None None None Do. 47. 37 None None Do. 44. 30 None None None 130. 39. O0 5 None None I!) o. 42. 27 None None None Passes 35. 53 None None None Do. 38. 33 5 2% 1 Fails. 49. 40 None None None Passes 42. 70 None None None Do. 44. 75 None None None Do. 47. 40 4% 3% 2%, Fails.

In the above table the numbered salts had the composition shown in the preceding Table I and the physical appearance and properties at 100% solid as indicated.

Certain of the salts listed in the table have good solubility characteristics and others have good surface tension reducing properties, some have good emulsifying properties, and some have good foaming properties, but only the normal Cs and C10 mixed mono and di ester ortho- 8 phosphoric acid salts (with m values of 1.3 to 1.7, both inclusive) listed have all four of these properties together. The unique balanced properties of these compounds cannot be predicted from the other members of this series. In this respect they are exceptions to the homologous series.

The general rule appears to be that the salts of the acid alkyl esters of the phospohric acids, whether they be meta, ortho, pyro or poly phosphates, are non-frothcrs or give unstable froths, and either non-emulsifiers or poor emulsifiers. The exception to this rule appears to be in the case of certain of those salts which have sufiicient dispersibiiity so that at least .05 by weight of the salts are dispcrsible to give stable dispersions in distilled water at about C. These salts are the ammonium and organo amine salts of the mono and di alkyl ortho-phosphates when the alkyl radical is normal C8 or C10. The only alkali metal salt among those listed in the table which has this property is the K salt of the normal Ca and C10 compounds.

The above table also showsthat the unique properties of the alkyl phosphates referred to above are the unique properties of the normal C8 and C10 ortho-phosphates in which the C-O-ester linkage is at the terminal C of the alkyl radical.

It will be observed that whereas the 2-amino-2-methyll-propanol salt of the mono and di normal octyl orthophosphate is a good surface tension depressant, a good emulsifier and foamer, the corresponding salts of the di normal octyl pyrophosphate and polyphosphate, while having approximately the same surface tension reducing properties and dispersibility in water, are non-emulsifiers and poor foamers or non-foamers.

For example, the isomeric octyl primary alcohols or the secondary octyl alcohols are not as a class suitable for the formation of the ester salts which have the useful properties of the ester salts made from the normal alkyl Cs ester salt where the ester linkage is on the terminal carbon of the alkyl Ca. Thus, Z-ethyl-hexanol-l was esterified with P205. A clear liquid resulted. Upon cooling it separates into two layers. The mixed layers were neutralized with 2 amino 2 methyl l propanol. This compound is dispersible and produced a foam in the above test which broke completely before one minute. Capryl alcohol was substantially uon-reactive with P205. No esterification was obtained to any substantial degree even at elevated temperatures.

Of the above normal alkyl Ca and C10 mono and di orthophosphate salts only the salts with organo amine cations are soluble or dispersible in hydrophobic and hydrophilic organic solvents. The ammonium salts form an exception to the salts of the inorganic cations in that they may be dispersed or dissolved in hydrophobic solvents provided that they contain small amounts of water and substantial quantities of residual solvents, as will be more fully set forth below.

The dispersibility of the organo amine salts of these mixed mono and di normal Ca and C10 ortho-phosphoric acids is also given in the following table:

TABLE II Solubility determinations REAGENTS USED IN NEUTRALIZATION of (11) OCIYL, (n) DEOYL MONO AND DI ALKYL ORTHO-PHOSPHORIC ACIDS Organic Solvents NaOH KOH NH4OH (CQHQZNH HOCzlLNHq (HOC:H4)2NH Morpholine P P 1? CS CS 08 CS P P P CS CS CS CS P P P CS OS OS OS I P P OS GS CS 05 P P P CS CS CS CS P P P CS CS OS OS 1,1,2 trichlorethane--- P P P OS OS CS CS Pine oil (farmer 302). P P P CS 08 CS CS Xylene P P P DS DS DS DS Aromatic-naphtha. P l? P DS DS DS DS Solvent to detergent: Ratio :5 by weight. Code: P=Precipitates (settles out); CS=fJlear so lutlon (stable); DS=Dim solution (light cloudiness). This condltion is easily cleared up by addition of small amounts of solvents designated OS, particularly oxygen bearing ones.

- It will be observed that the alkali metal and the am monium saltsare not dispersible in the ratio of salt to 95% solvent. In fact, as low as 2% solids will not give stable dispersion or solution. However, the organo amine salts are dispersible or soluble as shown in the table at such ratio and in fact miscible or'dispersible in substantially all proportions.

As stated above the ammonium salt is also dispersi- 7 Me in such solvent if a blending agent or a mutual sol vent, such as water and water soluble alkanol, is em ployed. We may thus employ a low molecular weight alkanol, i. e., lower'than butanol, or employ an equivalent alkanol compound such as the glycols or the ether glycols, for example, such mutual solvents as the monohydric alcohols, such as methyl alcohol, ethyl alcohol, propyl alcohol, or isopropylalcohol, or the polyhydric alcohols, such as glycol or glycerine, or their monoalkyl others, for example, ethylene glycol, propylene glycol, diethylene glycol, polyethyleneglycol, hexane-l-2 diol, the glycol ethers, such as ethyleneglycolmonoethyl ether, ethylene: glycolmonobutyl ether, ethyleneglycolmonopropyl ether.

Thus, for example, 5% of the ammonium salt of the mono and di normal octyl and the mono and di normal decyl orthophosphoric acid is dispersible in a solvent such-as one having 45% isopropanol, 45% xylene, and 5% water. The ammonium salt is susbtantially completely dispersible in this solvent composition in substantiallytall Weight proportions. Instead ofisopropanol We may use any of the otheralkanols listed above. Instead of xylene we may employ any one of the hydrophobic solvents listed inthe above table or any other hydrophobic, aliphatic, aromatic or chlorinated hydrocarbonsusually employed in the dry cleaning'art. The ratio of solvents may also be adjusted within wide limits depending upon the nature of the solvents employed and the. specific. salt as Well as the. cleaning service to which it: is: to. be applied.

The'property of dispersing in such solvents as here listed and which are commercially widely used in dry cleaning or laundering, in. addition to the properties of good? foaming, good wetting, and good emulsification in In order, therefore, to determine the suitability of the decyl ortho-phosphate neutralized with an organoamine.

water, make thesematerials available both for laundering and: dry cleaning operations and alsoin cleaning operations in'which' mixtures of hydrophobic solvents and 'water" are employed. 1 7

We have also found that the alkanol amides of the soap-forming fatty acids are useful/additives to laundering and dry cleaning fluidswhen employed with the ester salts of our invention, i; e.', the salts of the mixed normal octyl and decyl orth'o-phosphoric acids.

The alkanolamid'es of the acidswhich we have found useful are those of the acids found in cocoanut fatty acids and in the acids" derivable from ordinary kitchen grease or tall oil. These mixtures contain lauiic acid, myristicacid, palmitic acid, oleic acid, linoleic acid in predominant amounts and tall oil contains substantial amounts of abietic acid. Such acids form characteristic soaps by saponification with alkalies such as NaOH and;

may therefore be classified as soap-forming. These acids whether used in the crude. admixtures specified above or whether employed as pure acids, give with alkanol amines,

amides which are dispersible when introduced into water in finely divided state or as solutions: in organic solvents. We may thus employ the alkanol: amidesof the alkane, alkene orucycloalkene carboxylic soap-forming acids or acid mixtures thereof 'which acids or" acid=mixtures have a mean; molecular weight or neutralization equivalent of about 170 or higher and which are dispersible in water;

The dispersibility in water depends: notxonly on the nature of the acid but also on the nature of the alkanola mine. Thus, for example, monoethanolamide of cocoanut fatty acid has a much lower dispersibility in Water than the corresponding amide formed amino methane.

with tri-Ihyd'roxymethyl) 'to exceed 4 parts of amide to 1 part of ester salt.

A preferred test solution constitutes by weight: 16% amide of the fatty acid; 4% mono and di normal octyl phosphoric acid salt of 'diethanol amine (m approximately 1.5); 40% xylol; 40% isopropanol.

We pour 10 cc. of thissolution into cc. of distilled Water at a temperature of F. No precipitation of the amide must occur. Amide which meets these requirements istermed a water dispersible amide and one which is useful. One which does not pass the test is a non-dispersible amide and is not useful. These amides are substantially non-foamers as defined above. Neither are they emulsifiers nor are they surface tension reducers to a substantial degree. They cannot be used by themselves in laundering operations.

However, we have found that when used in combination with the foaming, emulsifying and wetting salts of the normal octyl or decyl mono. and di ortho-phosphates as described they have the property of enhancing the foaming and emulsifying properties of these orthophosphate compounds. Thus, we have found in practical laundering operations by numerous tests that we can obtain a superior laundering result by adding to the ortho-phosphates described above some of the water dis persible amides referred to above. In fact, the addition of this amide permits the reduction in concentration of the ortho-phosphate ester in the laundering andv dry cleaning fluid with an improved result over the higher concentrations of the ortho-phosphateester used without the addition of such amide. Two-thirds of the amide to one-third of the ester salt have proved. an excellent ratio. The ratio is not criticaland may be varied within wide limits, depending on the total concentration of reagent employed in the laundering and dry cleaning fluid, on the other constituents of the laundering solution, and on the natureof the amide and ester salt. For practical laundering purposes, when the amide is used for the purposes herestated, We have found that it is not desirable In order to get the benefits of the amide for the purposes here stated, we prefer to use not less than 1 part of amide to.4 parts of esterisalts. We may, of course, as stated above omit the amide and obtain highly useful results. In all of these mixtures the practical 'value' of the combination as a frothing, emulsifying solution is greater than where the'ester salt is used in the absence of the amide. Additionally, we find that when employing these mixtures We may obtain equal laundering and dry cleaning results with much lower total ester salt concentrations.

The above alkanolamides are waxy or pasty solids at room temperature and inorder to disperse them in water, we depend upon. their solubility in organic solvents such as those specified above. In order to compound these solvent solutions with the ester salts we desire to employ those ester salts which. are also soluble in such solvents. These ester salts are the organo amine salts specified above or the *NI-Lr 'salts described, provided the solvent base contains wateras wellas the other mutual s0lvents as described above, When such 'a solution ismade, it may be readily mixed with either the laundry water or the dry cleaning solvent-to form aclear stable dispersionor solution which willhave the desirable. wetting, foarning and detergent action characteristic of our invention.

Due to the fact that the ester salts of our invention are compatible with fatty acid soaps, We may employ "11 easily rinsed. Insolublealkali earth soaps are formed if hard water is employed. Soap for this reason is being replacedby synthetic detergents. We have found that we may add small proportions of soap without impairing the excellent foaming, emulsifying and wetting properties imparted by our ester salts and the resultant free and easy rinsibility of materials washed therewith. Soap, being a relatively inexpensive detergent, is thus a use ful additive, and due to the superior properties of. our compounds it will not seriously impair their properties if used in reasonable amounts in conjunction therewitl'i.

When soap is added to the laundering and dry cleaning batch independently of the addition of the reagents of our invention, sodium or K or NH; soaps may be used. However, if the soap is to be added to the com position containing the amides in the solvent solution. a soap which is dispersible in such mixture should he used. Thus, the sodium soap may not be used practically and the K or the NH4 soap is the more desirable soap to be used. Thus potassium oleate when added to the mixture is a highly useful additive.

To illustrate the high efiiciency of our form of laundering reagent as compared with soap, the following test data is herewith presented by Way of illustration and not as a limitation of our invention:

EXAMPLE 1 The laundering formula employed was: parts of monoethanolamide of cocoanut fatty acid; 6 parts mono and di normal octyl ortho-phosphoric acid salt of diethanolamine; 8 parts of a 50% solution potassium oleate in water; 35 parts of xylene; 35.5 parts of isopropanol.

The conditions of the test were as follows:

The clothes to be cleaned weighed 200 pounds in each test. The type of laundering material was the American Laundering Machinery Corporations rotary wash wheel, capacity 200 pounds, open pocket. 150 gallons of water softened by a Zeolite softening procedure were used to which two pounds of sodium ortho silicate and six ounces of tetrasodium polyphosphate were added in each run. These are conventional laundering ingredients to give higher pH and lime sequestering action. Parallel washing operations on the soiled cloth as tabulated below were run using the above laundering solution added to the water and also with addition of 88% of a good grade of commercial soap to the water.

The washing cycle was as follows: The cloth was first washed at 160 F. with wash water containing the laundering reagent (soap in one case, and the above formula in the other case) as shown in the table, and re-washed at 160 F. with the wash water containing a concentration of laundering reagentone-half that of the first wash water. All of the wash waters were, as stated, 150 gallons containing the polyphosphate and ortho silicate, as stated above. Following the second wash, after drainage, the cloth was rinsed twice with hot water and then given a conventional bleach with sodium hypochlorite, followed by rinsing and souring off. Except for the laundering reagent used in the wash water, all runs were identical.

Formula 1 used in ounces per 150 gallons- Soap used in ounces per 150 gallons 200 pound}? oil cloth r In the above tests the cloth in all cases was satisfactorily laundered white, free of specking, and was su-. perior in cases using Formula 1, particularly in the case of the pillow slips. This class of cloth is notoriously have the solvent balance referred to above.

12 hard to launder due to the hair oil and cosmetics which soil. such slips. The cloth in the case of the reagent of our inventionwas more free of odor than in the case of scap-washed cloth.

It will be observed that, depending on the nature of the cloth, the laundering reagent of Formula 1 is equally or more effective than soap in washing such cloth when the active ingredients are used in amounts equal to form .1 to .2 of the concentration of the anhydrous soap necessary for such Washing action.

The above results are also characteristic of the other ester salts and amides referred to above.

It has been found that in the case of Formula 1 as well as in all formulations using our ester salts, it is not necessary to make more than one washing operation. All of the laundering reagent may be added to the initial wash water and this first washing operation may be followed by rinsing operation. This eliminates one washing step.

It is desirable in formulating the. laundering and dry cleaning compound to incorporate an organic solvent or solvent mixture, especially when the phosphoric acid ester salt or the acid amide employed is of waxy or pasty substance, since by so doing its dispersibility in water is aided. However, in this case it is desirable to employ the organo amine salts of the mono and di alkylnormal Cs and C10 ortho-phosphoric acid salts, since they are dispersible or soluble in an organic solvent, or if the ammonium salt is employed the solvent employed should The phosphoric acid salts referred to, if they are of the desirable frothing and emulsifying properties referred to above, cause the ready emulsification of the organic solvent in the water employed in the laundering operation. Dry mixturesmay readily be made by mixture of the salts with a wide variety of alkalies, inorganic phosphate, borax, diatomaceous earth, clay and other salts or absorbing substances as have been used in the prior art laundering and detergency practice.

The following formulations are examples of detergents which may be used in the place of soap and other detergents to give good wetting action, excellent detergency, and emulsification and frothing properties to laundering solutions. The following are merely illustrative and are not limiting. The proportions which may be employed maybe varied over a wide range depending on the amount employed in the wash water and on the nature of the compositions. The. ratio of the amide to the ester salt should be from about 1 to 4 to 4 to l.

The ester salt may be any one of the above ester salts which are good foaming, emulsifying, and wetting agents and the amide maybe any one of the above alkanol amides stated to be useful for this purpose. The solvents may be any' one of the solvents stated above to be useful and the concentration of the amide and ester salt is one of convenience only, since the solvents are merely carriers for introducing the active detergent into the wash water:

Base A 30 parts high flash aromatic naphtha; 30 parts isopropyl alcohol; 7 parts monoethanolamide of cocoanut fatty acid; 3 parts diethanolamine salt of mono and di octyl orthophosphoric acid (88% solids solution in water). This is an amber colored liquid of low viscosity.

Dry powdered detergent mixtures may be made with Ease A as follows:

200 parts Base A; 400 parts clay; 400 parts soda ash.

225 parts Base A; 150 parts soda ash; 50 parts sodium tetraphosphate (NasPaOrs); 400 parts NazSiOznS H2O;

200 pounds Base B;

400 pounds clay;

17 pounds soda ash; I,

33 pounds tallow soap (88 active).

200 parts Base B; 400 parts soda ash; 400 parts clay.

Another type is: 7

Base C 38 parts high flash aromatic naphtha;

38 parts butyl Cellosolve (ethyleneglycol monobutyl ether); v

9 parts monoethanolamide of kitchen. grease fatty acid, whose acid number before amidification was 209 (alc. KOH) and after amidification the acid number was 2.4;

parts diethanolamine salt of mono and di decyl orthophosphoric acid;

10 parts potassium oleate (62.5% solids solution in water).

Whenever the term parts is used in the claims and specification, the proportions are weight proportions.

While we have described a particular embodiment of our invention for the purpose of illustration, it should be understood that various modifications and adaptations thereof may be made within the spirit of the invention as set forth in the appended claims.

We claim: 7 1 l. A laundering composition comprising a water dispersible alkanol amide of an acid chosen from thegroup consisting of the alkane, alkene, and cycloalkene carboxylic soap-forming acids and having a mean acid number of at least about 170, and a water dispersible mixture of salts of mono acid and diacid esters of orthophosphoric acid, said mixture complying with the general formula where R is a radical chosen from the group consisting of normal octyl and normal decyl radicals, and X is chosen from the group consisting of the alkali metal, ammonium, water soluble amine, and water soluble alkanol amine radicals, and where the C0 linkage of the RO group is on the terminal carbon of the alkyl radical, and Where m is within the range of approximately 1.3 to approximately 1.7.

2. A laundering composition comprising a water dispersible alkanol amide of an acid chosen from the group consisting of the alkane, alkene and cycloalkene carboxylic soap-forming acids and having a mean acid number of at least about 170, and a water dispersible mixture of salts of mono acid and diacid esters of ortho-phosw 1'4 phoric acid, said mixture complying with the general formula I /P0 h-m where X is a water soluble alkanol amine radical, R. is a radicalchosen from the group consisting of normal octyl and normal decyl radicals, where in the R0 group the terminal carbon of the alkyl radical is joined to oxygen in the C-O linkage, and wherein m is in the range of approximately 1.3 to approximately 1.7.

3. A laundering composition comprising a water dispersible alkanol amide of an acid chosen from the group consisting of the alkane, alkene and cycloalkene car boxylic soap-forming acids and having a mean acid number of at least about 170, and a water dispersible mixture of salts of mono acid and diacid esters of ortho phosphoric acid, said mixture complying with the general formula where X is diethanolamine radical, R is a radical chosen from the group consisting of normal octyl and normal decyl radicals, Where in the R0 group the terminal carbon of the alkyl radical is joined to oxygen in the CPO linkage, and wherein m is in the range of approximately 1.3 to approximately 1.7.

4. A laundering composition comprising a water dispersible alkanol amide of an acid'chosen from the group consisting of the alkane, alkene and cycloalkene' carboxylic soap-forming acids and having a mean acid number of at least about 170, and a water dispersible mixture of salts of mono acid and diacid esters of ortho-phosphoric acid having the general formula Where X is 2-amino-2-methyl propanol-l radical, R is a radical chosen from the group consisting of normal octyl and normal decyl radicals, where in the R0 group the terminal carbon of the alkyl radical is joined to oxygen in the C0 linkage, and wherein m is in the range of approximately 1.3 to approximately 1.7.

5. A laundering composition comprising monoethanol amide of cocoanut fatty acid and a water soluble mix ture of salts of mono acid and diacid esters of orthophosphoric acid, said mixture complying with the gen eral formula where R is a radical chosen from the group consisting of normal octyl and normal decyl radicals, and X is chosen from the group consisting of the alkali metal, ammonium, water soluble amine, and Water soluble alkanol amine radicals, and where the C0 linkage of the RO group is on the terminal carbon of the alkyl radical, and where m is within the range of approximately 1.3 to approximately 1.7.

6. A laundering composition comprising monoethanol amide of a cocoanut fatty acid and a water dispersible mixture of salts of mono acid and diacid esters of orthophosphoric acid, said mixture complying with the general formula /PO (ROM-M where X is a water soluble alkanol amine radical, R is a '15 radical chosen from the group consisting of normal octyl and normal decyl radicals, where in the RO group the terminal carbon of the alkyl radical is joined to oxygen in the C linkage, and wherein m is in the range of 1.3 to 1.7.

7. A laundering composition comprising monoethanol amide of a cocoanut fatty acid and a water dispersible diethanolamine salt of mixed mono acid and diacid esters of ortho-phosphoric acid having the general formula PO n-M where X is a water soluble alkanol amine radical, R is a radical chosen from the group consisting of normal octyl and normal decyl radicals, wherein the R0 group the terminal carbon of the alkyl radical is joined to oxygen in the C-O linkage, and wherein m is in the range of approximately 1.3 to approximately 1.7.

9. A laundering composition comprising monoisopropanol amide of cocoanut fatty acid and a water dispersible mixture of salts of diethanolamine, mono acid and diacid esters of ortho-phosphoric acid, said mixture complying with the general formula /PO (R n-m where X is the diethanolamine radical, R is a radical chosen from the group consisting of normal octyl and normal decyl radicals, where in the RO group the terminal carbon of the alkyl radical is joined to oxygen in the C--O linkage, and wherein m is in the range of 1.3 to 1.7.

10. A laundering composition comprising monoethanol amide of a cocoanut fatty acid and a. water dispersible mixture of salts of 2-amino-2-methyl propanol-l, mono acid and diacid esters of ortho-phosphoric, said mixture complying with the general formula )3-m where X is the 2-amino-2-methyl propanol-l radical, R is a radical chosen from the group consisting of normal octyl and normal decyl radicals, where in the R0 group the terminal carbon of the alkyl radicalis joined to oxygen in the C0 linkage, and wherein m is in the range of approximately 1.3 to approximately 1.7.

11. A laundering composition comprising monoisopropanol amide of a cocoanut fatty acid and a water dispersible mixture of salts of Z-amino-Z-methyl propanol-l, mono acid and diacid esters of ortho-phosphoric acid, said mixture complying with the general formula panol amide of lauric acid and a water dispersible fl'llX,

ture of salts of 2-amino-2-methyl propanol-l, mono acid and diacid esters of ortho-phosphoric acid, said mixture complying with the general formula (RO)3-m where X is the 2-amino-2-methyl propanol-l radical, R is a radical chosen from the group consisting of normal octyl and normal decyl radicals, where in the R0 group the terminal carbon of the alkyl radical is joined to oxygen in the C0 linkage, and wherein m is in the range of approximately 1.3 to approximately 1.7.

References Cited in the file of this patent UNITED STATES PATENTS 

1. A LAUNDERING COMPOSITION COMPRISING A WATER DISPERSIBLE ALKANOL AMIDE OF AN ACID CHOSEN FROM THE GROUP CONSISTING OF THE ALKANE, ALKENE, AND CYCLOALKENE CARBOXYLIC SOAP-FORMING ACIDS AND HAVING A MEANS ACID NUMBER OF AT LEAST ABOUT 170, AND A WATER DISPERSIBLE MIXTURE OF SALTS OF MONO ACID AND DIACID ESTERS OF ORTHOPHOSPHORIC ACID, SAID MIXTURE COMPLYING WITH THE GENERAL FORMULA 